Bioresource Technology 92 (2004) 7981

Adsorption of chromium from aqueous solution on treated sawdust

V.K. Garg
a

a,*

, Renuka Gupta a, Rakesh Kumar a, R.K. Gupta

Department of Environmental Science and Engineering, Guru Jambheshwar University, Hisar 125001, India
b
Department of Applied Chemistry, Guru Jambheshwar University, Hisar 125001, India
Received 20 March 2003; received in revised form 6 June 2003; accepted 10 July 2003

Abstract
The adsorption of Cr(VI) from aqueous solutions on formaldehyde treated sawdust (SD) and sulphuric acid treated sawdust
carbon (SDC) of Indian Rosewood, a timber industry waste, was studied at varying Cr(VI) concentrations, adsorbent dose, pH and
agitation time. Similar experiments were conducted with commercially available coconut based activated carbon to compare the
results. The Cr(VI) adsorption eciency on SDC was higher than SD. The adsorption followed rst order rate expression and
Lagergren equation. An initial pH of 3.0 was most favorable for Cr(VI) removal by both the adsorbents. Maximum Cr(VI) was
sequestered from the solution within 60 min after the beginning for every experiment. It is proposed that SDC and SD can be
potential adsorbents for Cr(VI) removal from dilute solutions.

2003 Elsevier Ltd. All rights reserved.
Keywords: Cr(VI); Formaldehyde; Sulphuric acid; Sawdust; Adsorption; Batch mode

1. Introduction
Chromium, in its hexavalent form, is one of the undesirable heavy metals because it aects human physiology accumulates in the food chain and cause several
ailments (Park and Jung, 2001). The main industrial
sources of chromium pollution are leather tanning,
electroplating, metal processing, wood preservatives,
paint and pigments, textile, dyeing, steel fabrication and
canning industry (Raji and Anirudhan, 1997). According to Indian standards, the permissible limit of Cr(VI)
for industrial euents to be discharged to surface water
is 0.1 mg/l. So the removal of Cr(VI) from industrial
euents is important before discharging them into
aquatic environments or on to land. A wide range of
physical and chemical processes is available for the removal of Cr(VI) from wastewater. However these
methods are ineective for Cr(VI) concentrations lower
than 100 mg/l and prohibitively costly (Matheichal et al.,
1997).
Adsorption on activated carbon (ACR) has been
found to be an eective process for Cr(VI) removal, but
it is too expensive. Consequently numerous low cost
*

Corresponding author. Fax: +91-1662-276240.

E-mail address: vinodkgarg@yahoo.com (V.K. Garg).

0960-8524/$ - see front matter
2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2003.07.004

alternatives have been studied including Casurina leaves

(Ranganathan, 2000), leaf mould (Sharma and Forster,
1994), moss peat (Sharma and Forster, 1995), green algae (Gupta et al., 2001), activated carbon bers (Park
and Jung, 2001) coconut waste (Selvi et al., 2001), rubber wood (Raji and Anirudhan, 1997) etc. New economical, easily available and highly eective adsorbents
are still needed. Saw dust is a waste by-product of the
timber industry that is either used as cooking fuel or a
packing material. The objective of this work was to
evaluate the adsorption capacity of Cr(VI) from aqueous solutions by sawdust of Indian Rosewood pretreated with formaldehyde and sulphuric acid by
varying Cr(VI) concentration, adsorbent dose, pH and
contact time and desorption.

2. Methods
2.1. Preparation of formaldehyde treated sawdust (SD)
Sawdust of Indian Rosewood (Dalbergia sissoo) collected from a local saw mill was dried in sunlight and
ground to a ne powder. To immobilize the color
and water-soluble substances the ground powder was
treated with 1% formaldehyde in the ratio of 1:5

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V.K. Garg et al. / Bioresource Technology 92 (2004) 7981

(SD:formaldehyde, w/v) at 50 C for 4 h. The sawdust

was ltered out, washed with distilled water to remove
free formaldehyde and activated at 80 C in a hot air
oven for 24 h. The resulting material was ground followed by sieving in the size range of 2050 mesh ASTM.
The material was placed in an airtight container for
further use.
2.2. Preparation of sulphuric acid treated sawdust carbon
(SDC)
One part of dried SD was mixed with one part of
concentrated sulphuric acid and heated in a mue furnace for 24 h at 150 C. The heated material was washed
with distilled water and soaked in 1% sodium bicarbonate solution overnight to remove residual acid. The
material was dried in an oven at 105 C for 24 h, ground
and sieved in the size range of 2050 mesh ASTM and
used for the further study. The various physico-chemical
characteristics of SDC were: apparent density 1.45 g/
ml; ash content 1.68%; moisture content 3.80%;
CEC 0.68 meq/g; water-soluble matter 1.68%; acid
soluble matter 9.34% and EC 0.10 mS/cm. All adsorbents were dried at 110 C overnight before the adsorption experiments.
Commercially available ACR was supplied by S.D.
Fine Chemicals, Mumbai, India and used as such
without further grinding and sieving.
2.3. Preparation of Cr(VI) solution
An accurately weighed quantity of the K2 Cr2 O7 was
dissolved in double-distilled water to prepare a stock
solution (1000 mg/l). Experimental solutions of the desired concentrations were obtained by successive dilutions. Experiments were carried out at initial pH values
ranging from 2.0 to 10.0; initial pH was controlled by
addition of dilute HCl or NaOH solutions.

3. Results and discussion

3.1. Eect of pH on Cr(VI) removal
Initial pH of Cr(VI) solution was increased after the
equilibrium time (3 h). The pH increase was lesser at
lower initial pH values. It may be due to hydrolysis of
the adsorbent in water, which will create positively
charged sites (Dakiky et al., 2002). Percentage removal
of Cr(VI) was maximum at the initial pH of 3.0 (99.7%,
86.6% and 62.2% by ACR, SDC and SD respectively)
and decreased at lower and higher initial pH values (Fig.
1). At initial pH of 3.0, the adsorbent surfaces might be
highly protonated which favor the uptake Cr(VI) in the
predominant anionic form (HCrO

4 ) (Srinivas Rao et al.,
1992). With increase in pH from 3 to 10, the degree of
protonation of carbon surfaces reduced gradually and
hence removal was decreased.
3.2. Eect of initial Cr(VI) concentration and contact
time
The eect of Cr(VI) concentration on the adsorption
by ACR, SDC and SD was investigated by varying the
initial Cr(VI) concentration (25, 50, 100, 150 and 200
mg/l) at initial pH of 3.0 for dierent time intervals.
Cr(VI) removal by ACR was 100% at all the studied
concentrations. Percent Cr(VI) removal eciency of
SDC and SD reduced with increase in Cr(VI) concentration. Cr(VI) uptake was reduced for SDC from 99.8%
to 74.8% and for SD from 87.8% to 36.2% as concentration was increased from 25 to 200 mg/l. Adsorption
and initial Cr(VI) concentration correlation was exponential in nature for SDC and SD. Though the percentage removal was decreased with increase in Cr(VI)
120

ACR
SDC
SD

100

In each adsorption experiment, 100 ml of Cr(VI) solution of known concentration and pH value was added
to 400 mg of SD, SDC or ACR in a 250 ml round
bottomed ask at room temperature (26 1 C) and the
mixture was stirred on a rotary orbital shaker at 160
rpm. The samples were withdrawn from the shaker at
the pre-determined time intervals, and adsorbent was
removed from the solution by centrifugation at 4500
rpm for 5 min. The residual Cr(VI) concentration in
supernatant was estimated calorimetrically with 1,5diphenylcarbazide at 540 nm. The experiments were
done by varying the amount of adsorbent (0.21.0 g/100
ml); Cr(VI) concentration in the solution (25200 mg/l)
at initial pH of 3.0 at dierent time intervals.

Percent Cr(VI) removal

2.4. Adsorption experiments

80

60

40

20

0
0

10

11

pH
Fig. 1. Eect of pH on Cr(VI) removal by ACR, SDC and SD (initial
Cr(VI) concentration 100 mg/l, adsorbent dose 0.4 g/100 ml, temperature 26 C, contact time 180 min).

V.K. Garg et al. / Bioresource Technology 92 (2004) 7981

concentration but the actual amount of Cr(VI) adsorbed

per unit mass of the adsorbent was increased. This accords well with the ndings of other investigator
(Ranganathan, 2000). The equilibrium was established
quickly within 15 min by ACR. However SDC and SD
took @60 and @180 min respectively for equilibrium attainment. The results also indicated that the time taken
to reach equilibrium was longer at higher concentrations.
3.3. Eect of adsorbent dose and contact time
The eect of adsorbent dose on Cr(VI) uptake was
investigated by varying the adsorbent dose (0.2, 0.4, 0.6,
0.8 and 1.0 g/100 ml) at initial pH of 3.0 for dierent
time intervals. The percent adsorption increased from
65.4% to 100%, as the SDC dose was increased (0.21.0
g/100 ml) after equilibrium time (3 h). For SD adsorption increased from 50.7% to 92.2% with similar doses.
ACR had 100% adsorption at all the studied doses. Increase in adsorption with dose can be attributed to increased surface area and the availability of more
adsorption sites. For SDC, unit adsorption density was
decreased from 3.7 to 10.0 mg/g as the dose was increased from 0.2 to 1.0 g/100 ml in the solution. This
may be due to aggregation of adsorption sites resulting
in decrease in total adsorbent surface area of carbon
particles available to Cr(VI) and an increase in diusion
path length. For SD, the adsorption density was lesser
(25.49.2 mg/g) than SDC with similar doses. Equilibrium time was lesser at higher adsorbent doses.
The specic rate constants, Kad , for the adsorption of
Cr(VI) on SDC and SD were determined using the
pseudo-rst order Lagergren equation. The straight-line
plot of logqe
q versus
t at dierent adsorbent doses
conrmed the validity of the Lagergren equation and
also explained that process followed the pseudo-rst
order kinetics. The values of Kad , calculated from the
slopes of the plots were 0.026 and 0.038 min
1 for SDC;
and 0.019 and 0.023 min
1 for SD at 0.2 and 0.4 g doses
per 100 ml. These values showed that adsorption was
faster at the higher adsorbent doses.
3.4. Desorption of Cr(VI)
Desorption studied are helpful to explore the possibility of recycling the adsorbents and recovery of metal
resource. From SDC and SD used for 100 mg/l Cr(VI)
solution, 48% and 42% Cr(VI) was desorbed by 1 N
NaOH HCl was used to desorb the remaining Cr(VI).

81

The total Cr(VI) released was 72% and 66% for SDC
and SD respectively.

4. Conclusion
New alternative adsorbents for Cr(VI) removal have
been explored by making simple chemical modications
of sawdust by formaldehyde and sulphuric acid. This
study showed that SDC and SD had lower adsorption
eciency than ACR at higher Cr(VI) concentrations.
Initial pH of 3.0 was optimum for maximum Cr(VI)
removal by SDC and SD. At higher and lower initial pH
values than 3.0, adsorption of Cr(VI) was decreased
sharply. Higher removal by SDC and SD was possible
provided the Cr(VI) concentration was low in the solution. SD is easily available in the countryside, so can be
used by small scale industries having low concentrations
of Cr(VI) in wastewater using batched or stirred-tank
ow reactors after treating it with formaldehyde or
sulphuric acid.

References
Dakiky, M., Khamis, M., Manassra, A., Mereb, M., 2002. Selective
adsorption of chromium (VI) in industrial wastewater using low
cost abundantly available adsorbents. Adv. Environ. Res. 6, 533
540.
Gupta, V.K., Shrivastava, A.K., Jain, N., 2001. Biosorption of
chromium (VI) from aqueous solutions by green algae spirogyra
species. Water Res. 35 (17), 40794090.
Matheichal, J.T., Yu, Q., Feltham, J., 1997. Cu(II) binding by E.
radiata biomaterial. Environ. Technol. 18, 2534.
Park, S., Jung, W.Y., 2001. Removal of chromium by activated carbon
bers plated with copper metal. Carbon Sci. 2 (1), 1521.
Raji, C., Anirudhan, T.S., 1997. Chromium (VI) adsorption by
sawdust: kinetics and equilibrium. Indian J. Chem. Technol. 4,
228236.
Ranganathan, K., 2000. Chromium removal by activated carbons
prepared from Casurina equisatifolia leaves. Bioresour. Technol.
73, 99103.
Selvi, K., Pattabhi, S., Kadirvelu, K., 2001. Removal of Cr(VI) from
aqueous solution by adsorption onto activated carbon. Bioresour.
Technol. 80, 8789.
Sharma, D.C., Forster, C.F., 1994. The treatment of chromium
wastewater using the sorptive potential of leaf mould. Bioresour.
Technol. 49, 3140.
Sharma, D.C., Forster, C.F., 1995. Column studies into the adsorption
of chromium (VI) using sphagnum moss peat. Bioresour. Technol.
52, 261267.
Srinivas Rao, P., Shashikant, R., Munjunatha, G.S., 1992. Kinetic
studies on adsorption of chromium by coconut shell carbons
from synthetic euents. J. Environ. Sci. Health A 27 (8), 2227
2241.